CN107406681B - Curable resin composition, dry film, cured product, and printed wiring board - Google Patents
Curable resin composition, dry film, cured product, and printed wiring board Download PDFInfo
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- CN107406681B CN107406681B CN201580078123.XA CN201580078123A CN107406681B CN 107406681 B CN107406681 B CN 107406681B CN 201580078123 A CN201580078123 A CN 201580078123A CN 107406681 B CN107406681 B CN 107406681B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
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Abstract
The invention provides a curable resin composition, a dry film, a cured product and a printed circuit board, wherein the curable resin composition has high reflectivity in addition to the characteristics of a solder resist such as soldering heat resistance. A curable resin composition comprising (A) a curable resin, (B) a white colorant, (C) a fluorescent whitening agent, and (D) at least one member selected from the group consisting of isocyanate compounds and coupling agents. A dry film comprising a resin layer obtained by applying the curable resin composition to a film and drying the film. A cured product obtained by curing the curable resin composition or a resin layer obtained by applying and drying the curable resin composition. A printed wiring board having the cured product.
Description
Technical Field
The present invention relates to a curable resin composition (hereinafter, also simply referred to as "composition"), a dry film, a cured product, and a printed wiring board, and more particularly, to a curable resin composition, a dry film, a cured product, and a printed wiring board, which have improved reflectance.
Background
In general, a printed circuit board is obtained by etching a copper foil bonded to a laminate sheet according to circuit wiring, arranging electronic components at predetermined positions, and soldering the electronic components. Solder resists are used as protective films for circuits when electronic components are soldered to such printed wiring boards. The solder resist film can prevent solder from adhering to an unnecessary portion during soldering, and can prevent a circuit conductor from being directly exposed to air and thus being corroded by oxidation or moisture. Further, the film also functions as a permanent protective film for the circuit board. Therefore, various properties such as adhesion, electrical insulation, soldering heat resistance, solvent resistance, and chemical resistance are required.
Printed circuit boards are being miniaturized, multilayered, and single-board (one board) to achieve higher density, and mounting methods are also being shifted to Surface Mount Technology (SMT). Therefore, the solder resist film is also required to be fine, high in resolution, high in precision, and high in reliability.
As a technique for forming a pattern of such a solder resist, a photoresist method capable of forming a fine pattern with accuracy, particularly, an alkali development type liquid photoresist method has become mainstream from the viewpoint of environmental considerations and the like.
For example, patent documents 1 and 2 disclose a liquid protective ink (resist ink) composition which can be developed in an alkaline aqueous solution, and which has a reaction product obtained by reacting an unsaturated monocarboxylic acid with a novolak-type epoxy resin and further adding a polybasic acid anhydride as a base polymer.
On the other hand, in recent years, there has been an increasing use of directly mounting Light Emitting Diodes (LEDs) emitting light at low power, such as backlights of liquid crystal displays of mobile terminals, personal computers, televisions, and the like, and light sources of lighting fixtures, on a printed wiring board coated with a solder resist.
Therefore, in order to effectively use the light of the LED, a printed circuit board having a solder resist film with a high reflectance is desired.
As a technique for improving the reflectance of a solder resist, for example, patent document 3 discloses a white curable solder resist composition containing a carboxyl group-containing resin having no aromatic ring and rutile type titanium oxide.
Documents of the prior art
Patent document
Patent document 1: japanese examined patent publication (Kokoku) No. 1-54390
Patent document 2: japanese examined patent publication (Kokoku) No. 7-17737
Patent document 3: japanese laid-open patent publication No. 2007-322546
Disclosure of Invention
Problems to be solved by the invention
However, the conventional compositions described in patent documents 1 to 3 have both sufficient solder resist properties such as solder heat resistance and have room for improvement in obtaining high reflectance.
Accordingly, an object of the present invention is to provide a curable resin composition, a dry film, a cured product, and a printed wiring board, which have high reflectance in addition to characteristics as a solder resist such as solder heat resistance.
Means for solving the problems
The inventors of the present invention conducted extensive studies and found that: the present inventors have found that a high reflectance can be achieved in addition to the characteristics as a solder resist such as solder heat resistance by using a white colorant such as titanium oxide, a fluorescent whitening agent, and at least one member selected from an isocyanate compound and a coupling agent in combination for a curable resin composition, and have completed the present invention.
That is, the curable resin composition of the present invention is characterized by containing (a) a curable resin, (B) a white colorant, (C) a fluorescent whitening agent, and (D) at least one selected from an isocyanate compound and a coupling agent.
The dry film of the present invention is characterized by having a resin layer obtained by applying and drying the curable resin composition of the present invention to a film.
Further, the cured product of the present invention is obtained by curing the curable resin composition of the present invention or a resin layer obtained by applying the curable resin composition of the present invention and drying the applied resin layer.
The printed wiring board of the present invention is characterized by having the cured product of the present invention.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a curable resin composition, a dry film, a cured product, and a printed wiring board can be realized which have both high reflectance and solder resist properties such as solder heat resistance.
Drawings
Fig. 1 is a graph showing the relationship between the wavelength and the reflectance of each composition of examples 2 and 3 and comparative example 2.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail.
The curable resin composition of the present invention is characterized in that: comprises (A) a curable resin, (B) a white colorant, (C) a fluorescent whitening agent, and (D) at least one member selected from the group consisting of isocyanate compounds and coupling agents. Thus, a curable resin composition having high reflectance in addition to the characteristics as a solder resist such as solder heat resistance can be obtained.
Next, each component of the curable resin composition of the present invention will be described. In the present specification, the term (meth) acrylate refers to a general term of acrylate, methacrylate and a mixture thereof, and the same applies to other similar expressions.
[ (A) curable resin ]
The curable resin composition of the present invention contains (a) a curable resin. The curable resin (A) used in the present invention is a thermosetting resin (A-1) or a photocurable resin (A-2), and may be a mixture thereof.
((A-1) thermosetting resin)
The thermosetting resin (a-1) may be a resin which is cured by heating and exhibits electrical insulation, and examples thereof include: epoxy compounds, oxetane compounds, melamine resins, silicone resins, and the like. In particular, in the present invention, an epoxy compound and an oxetane compound can be suitably used, and they can be used in combination.
As the epoxy compound, known and conventional compounds having 1 or more epoxy groups can be used, and among them, compounds having 2 or more epoxy groups are preferable. Examples thereof include: a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, glycidyl (meth) acrylate, a bisphenol a type epoxy resin, a bisphenol S type epoxy resin, a bisphenol F type epoxy resin, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, an alicyclic epoxy resin, trimethylolpropane polyglycidyl ether, phenyl-1, 3-diglycidyl ether, biphenyl-4, 4' -diglycidyl ether, 1, 6-hexanediol diglycidyl ether, diglycidyl ether of ethylene glycol or propylene glycol, sorbitol polyglycidyl ether, tris (2, 3-epoxypropyl) isocyanurate, triglycidyl tris (2-hydroxyethyl) isocyanurate, or the like having 2 or more epoxy groups in 1 molecule. They may be used alone or in combination of 2 or more depending on the required characteristics.
Next, the oxetane compound will be described. Specific examples of the oxetane compound containing an oxetane ring represented by the following general formula (I) include: 3-ethyl-3-hydroxymethyloxetane (trade name OXT-101, manufactured by Toyo Kabushiki Kaisha), 3-ethyl-3- (phenoxymethyl) oxetane (trade name OXT-211, manufactured by Toyo Kabushiki Kaisha), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane (trade name OXT-212, manufactured by Toyo Kabushiki Kaisha), 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene (trade name OXT-121, manufactured by Toyo Kabushiki Kaisha), bis (3-ethyl-3-oxetanylmethyl) ether (trade name OXT-221, manufactured by Toyo Kabushiki Kaisha), and the like. Further, an oxetane compound of phenol novolac type and the like can be given. These oxetane compounds may be used in combination with the above epoxy compounds or may be used alone.
(in the formula, R1Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atomsBase)
((A-2) Photocurable resin)
Next, the photocurable resin (a-2) may be a resin which is cured by irradiation with an active energy ray and exhibits electrical insulation, and in the present invention, a compound having 1 or more ethylenically unsaturated bonds in the molecule is particularly preferably used.
As the compound having an ethylenically unsaturated bond, a known and conventional photopolymerizable oligomer, a photopolymerizable vinyl monomer, or the like can be used. Among these, examples of the photopolymerizable oligomer include unsaturated polyester oligomers and (meth) acrylate oligomers. Examples of the (meth) acrylate oligomer include: epoxy (meth) acrylates such as phenol novolac epoxy (meth) acrylate, cresol novolac epoxy (meth) acrylate, bisphenol type epoxy (meth) acrylate, urethane (meth) acrylate, epoxy urethane (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate, polybutadiene-modified (meth) acrylate, and the like.
As the photopolymerizable vinyl monomer, known and commonly used ones can be mentioned, for example, styrene derivatives such as styrene, chlorostyrene and α -methylstyrene, vinyl esters such as vinyl acetate, vinyl butyrate and vinyl benzoate, vinyl ethers such as vinyl isobutyl ether, vinyl-N-butyl ether, vinyl-t-butyl ether, vinyl-N-pentyl ether, vinyl isoamyl ether, vinyl-N-octadecyl ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether and triethylene glycol monomethyl vinyl ether, (meth) acrylamides such as acrylamide, methacrylamide, N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, N-methoxymmethacrylamide, N-ethoxymethacrylamide and N-butoxymethacrylamide, (meth) acrylamides, allyl compounds such as triallyl isocyanurate, diallyl phthalate and diallyl isophthalate, (meth) acrylates such as 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, phenoxyethyl (meth) acrylate, (meth) acrylates such as trimethylolpropane (meth) acrylate, trimethylolpropane (pentaerythritol (meth) acrylate, trimethylolpropane (pentaerythritol (meth) acrylate, trimethylolpropane (bis (meth) acrylate, trimethylolpropane (ethylene glycol bis (meth) acrylate, pentaerythritol (meth) acrylate, trimethylolpropane (bis (meth) acrylate, pentaerythritol (bis (meth) acrylate, trimethylolpropane) acrylate, pentaerythritol (bis (meth) acrylate, and the like can be used in combination with the use of these (meth) acrylates, trimethylolpropane methacrylate, trimethylolpropane) acrylate, trimethylolpropane methacrylate, and the like, trimethylolpropane (meth) acrylate, trimethylolpropane methacrylate, trimethylolpropane (1-trimethylolpropane) acrylate, and the like, trimethylolpropane (meth) acrylate, trimethylolpropane methacrylate, and the like, and the specific examples of the use as the trimethylolpropane (meth) acrylate, the acrylic acid glycol bis (meth) acrylate, the acrylic acid ester of the acrylic acid ester, the acrylic acid ester of the.
((A-3) carboxyl group-containing resin)
In the composition of the present invention, when the composition of the present invention is made into an alkali-developable photosensitive resin composition by promoting a thermosetting reaction with an epoxy resin, a carboxyl group-containing resin is preferably used as the curable resin (a). The carboxyl group-containing resin may be a carboxyl group-containing photosensitive resin having an ethylenically unsaturated group, and may or may not have an aromatic ring.
Specific examples of the carboxyl group-containing resin that can be used in the composition of the present invention include the following compounds (both oligomers and polymers).
(1) The carboxyl group-containing resin is obtained by copolymerizing an unsaturated carboxylic acid such as (meth) acrylic acid with an unsaturated group-containing compound such as styrene, α -methylstyrene, a lower alkyl (meth) acrylate, or isobutylene.
(2) The carboxyl group-containing polyurethane resin is obtained by addition polymerization of a diisocyanate such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate, a carboxyl group-containing diol compound such as dimethylolpropionic acid or dimethylolbutyric acid, and a diol compound such as a polycarbonate-based polyol, a polyether-based polyol, a polyester-based polyol, a polyolefin-based polyol, an acrylic polyol, a bisphenol a-based alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group. When the carboxyl group-containing polyurethane resin has an aromatic ring, at least one of the diisocyanate, the carboxyl group-containing diol compound, and the diol compound may have an aromatic ring.
(3) A carboxyl group-containing urethane resin obtained by addition polymerization of a diisocyanate compound such as an aliphatic diisocyanate, a branched aliphatic diisocyanate, an alicyclic diisocyanate, or an aromatic diisocyanate with a diol compound such as a polycarbonate polyol, a polyether polyol, a polyester polyol, a polyolefin polyol, an acrylic polyol, a bisphenol a alkylene oxide adduct diol, or a compound having a phenolic hydroxyl group and an alcoholic hydroxyl group, and reacting the terminal of the urethane resin with an acid anhydride. When the carboxyl group-containing polyurethane resin has an aromatic ring, at least one of the diisocyanate compound, the diol compound, and the acid anhydride may have an aromatic ring.
(4) A photosensitive carboxyl group-containing polyurethane resin obtained by addition polymerization of a diisocyanate with a (meth) acrylate of a 2-functional epoxy resin such as a bisphenol a epoxy resin, a hydrogenated bisphenol a epoxy resin, a bisphenol F epoxy resin, a bisphenol S epoxy resin, a bixylenol epoxy resin, a bidiphenol epoxy resin, or the like, or a modified product of a partial acid anhydride thereof, a carboxyl group-containing diol compound, and a diol compound. When the photosensitive carboxyl group-containing urethane resin has an aromatic ring, at least one of diisocyanate, a (meth) acrylate of a 2-functional epoxy resin or a modified product of a partial acid anhydride thereof, a carboxyl group-containing diol compound, and a diol compound may have an aromatic ring.
(5) The carboxyl group-containing polyurethane resin obtained by adding a compound having one hydroxyl group and one or more (meth) acryloyl groups in a molecule, such as hydroxyalkyl (meth) acrylate, to the synthesis of the resin of (2) or (4) above and carrying out terminal (meth) acrylation. In the case where the photosensitive carboxyl group-containing polyurethane resin has an aromatic ring, the compound having one hydroxyl group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
(6) The carboxyl group-containing polyurethane resin is obtained by adding a compound having one isocyanate group and one or more (meth) acryloyl groups in a molecule, such as an equimolar reaction product of isophorone diisocyanate and pentaerythritol triacrylate, to the synthesis of the resin of the above (2) or (4) to carry out terminal (meth) acrylation. In the case where the photosensitive carboxyl group-containing polyurethane resin has an aromatic ring, the compound having one isocyanate group and one or more (meth) acryloyl groups in the molecule may have an aromatic ring.
(7) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin with (meth) acrylic acid and adding a hydroxyl group present in a side chain to a dibasic acid anhydride such as phthalic anhydride, tetrahydrophthalic anhydride or hexahydrophthalic anhydride. When the photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the polyfunctional epoxy resin and the dibasic acid anhydride may have an aromatic ring.
(8) A photosensitive carboxyl group-containing resin obtained by reacting a polyfunctional epoxy resin obtained by further epoxidizing the hydroxyl group of a 2-functional epoxy resin with (meth) acrylic acid by epichlorohydrin and adding the resulting hydroxyl group to a dibasic acid anhydride. When the photosensitive carboxyl group-containing resin has an aromatic ring, at least one of the 2-functional epoxy resin and the dibasic acid anhydride may have an aromatic ring.
(9) A carboxyl group-containing polyester resin obtained by reacting a polyfunctional oxetane resin with a dicarboxylic acid and adding the resulting primary hydroxyl group to a dibasic acid anhydride. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of the polyfunctional oxetane resin, the dicarboxylic acid and the dicarboxylic anhydride may have an aromatic ring.
(10) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with an alkylene oxide such as ethylene oxide or propylene oxide with an unsaturated group-containing monocarboxylic acid and reacting the resulting reaction product with a polybasic acid anhydride.
(11) A carboxyl group-containing photosensitive resin obtained by reacting a reaction product obtained by reacting a compound having a plurality of phenolic hydroxyl groups in 1 molecule with a cyclic carbonate compound such as ethylene carbonate or propylene carbonate with an unsaturated group-containing monocarboxylic acid and reacting the obtained reaction product with a polybasic acid anhydride.
(12) A carboxyl group-containing photosensitive resin is obtained by reacting an epoxy compound having a plurality of epoxy groups in 1 molecule, a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule such as p-hydroxyphenylethanol, and an unsaturated group-containing monocarboxylic acid such as (meth) acrylic acid, and reacting the alcoholic hydroxyl group of the reaction product thus obtained with a polybasic acid anhydride such as maleic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, or adipic anhydride. When the photosensitive carboxyl group-containing polyester resin has an aromatic ring, at least one of an epoxy compound, a compound having at least 1 alcoholic hydroxyl group and 1 phenolic hydroxyl group in 1 molecule, an unsaturated group-containing monocarboxylic acid, and a polybasic acid anhydride may have an aromatic ring.
(13) The photosensitive carboxyl group-containing resin is obtained by further adding a compound having one epoxy group and one or more (meth) acryloyl groups in the molecule, such as glycidyl (meth) acrylate or α -methylglycidyl (meth) acrylate, to any of the resins (1) to (12) above.
Since the carboxyl group-containing resin as described above has a plurality of carboxyl groups in the side chain of the main chain polymer, development can be performed with a dilute aqueous alkali solution.
Among the above, the carboxyl group-containing resin obtained by copolymerization in (1) is preferable in terms of suppressing a decrease in reflectance due to heat and suppressing discoloration. Further, the use of a carboxyl group-containing resin derived from styrene or a styrene derivative is preferable because a composition having excellent resistance to heat for welding can be obtained. Further, among the carboxyl group-containing resins, a composition having excellent solder heat resistance can be obtained even when a non-photosensitive resin is used, and therefore, such a resin is preferable.
The acid value of the carboxyl group-containing resin is preferably in the range of 20 to 200mgKOH/g, more preferably in the range of 40 to 180 mgKOH/g. When the content is in the range of 20 to 200mgKOH/g, the adhesiveness of the coating film can be obtained, the alkali development is easy, the dissolution of the exposed portion by the developer can be suppressed, the line is not as thin as necessary or more, and the normal resist pattern can be easily drawn, which is preferable.
The weight average molecular weight of the carboxyl group-containing resin used in the present invention varies depending on the resin skeleton, and is preferably in the range of 2000 to 150000. When the amount is in this range, the non-sticking property is good, the moisture resistance of the coating film after exposure is good, and film loss is less likely to occur during development. In addition, if the weight average molecular weight is within the above range, the resolution is improved, the developability is good, and the storage stability is good. More preferably 5000 to 100000. The weight average molecular weight can be determined by gel permeation chromatography.
When an epoxy resin and a carboxyl group-containing resin are used in combination as the curable resin (a), the yellowing resistance is good when the equivalent of an epoxy group contained in the epoxy resin is 2.0 or less relative to 1 equivalent of a carboxyl group contained in the carboxyl group-containing resin, and is preferably 1.5 or less, and more preferably 1.0 or less. This is because when an epoxy group is contained, discoloration tends to occur easily.
[ (B) white colorant ]
Examples of the white colorant (B) include: titanium oxide, zinc oxide, potassium titanate, zirconium oxide, antimony oxide, lead white, zinc sulfide, lead titanate, and the like, and titanium oxide is preferably used because of its high effect of suppressing discoloration due to heat. By containing (B) a white colorant, the composition of the present invention can be rendered white and a high reflectance can be obtained.
The titanium oxide may have any structure of rutile type, anatase type, and ramsdellite type, and 1 kind may be used alone or 2 or more kinds may be used in combination. Wherein the ramsdellite type titanium oxide can be prepared by subjecting ramsdellite type Li to0.5TiO2And subjected to a lithium desorption treatment by chemical oxidation.
Among the above, rutile titanium oxide is preferable because it is possible to further improve heat resistance, and it is difficult to cause discoloration by light irradiation, and it is difficult to reduce quality even in a severe use environment. In particular, rutile titanium oxide surface-treated with aluminum oxide such as alumina or silica can be used to suppress deterioration with light or to further improve reflectance and heat resistance. In addition to the above surface treatment, other surface treatments may be further performed. In particular, the reflectance can be further improved by performing a surface treatment with zirconia in addition to the surface treatment with alumina. When titanium oxide is used as the white colorant (B), the content of rutile-type titanium oxide surface-treated with aluminum oxide in the entire titanium oxide is preferably 10% by mass or more, more preferably 30% by mass or more, and the upper limit is 100% by mass or less, that is, the total amount of titanium oxide may be the rutile-type titanium oxide surface-treated with aluminum oxide. The rutile type titanium oxide surface-treated with aluminum oxide includes, for example: CR-58 available from Shikoku corporation as rutile type titanium oxide obtained by the chloride process, R-630 available from Shikoku corporation as rutile type titanium oxide obtained by the sulfate process, and the like. Further, rutile type titanium oxide surface-treated with silicon oxide is also preferably used, and in this case, heat resistance can be further improved. Further, rutile type titanium oxide surface-treated with both aluminum oxide and silicon oxide is preferably used, and examples thereof include CR-90 available from Shikoku Kogyo Co., Ltd as rutile type titanium oxide by the chlorine method.
Since anatase titanium oxide has lower hardness than rutile titanium oxide, the use of anatase titanium oxide is more favorable in terms of the moldability of the composition.
Further, although sulfur may be contained in titanium oxide, the amount of sulfur is preferably 100ppm or less, and more preferably 60ppm or less. This is because when the sulfur content is 100ppm or less, the color change of the peripheral portion due to the generated sulfur gas does not occur.
The amount of the white colorant (B) is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, based on the solid content of the resin composition (when the resin composition contains an organic solvent, the organic solvent is not included).
[ (C) fluorescent whitening agent ]
The fluorescent whitening agent (C) used in the present invention is a substance that can increase the whiteness of a cured product of the composition and exhibit no discoloration. In the present invention, as described above, by using (B) a white colorant and (C) a fluorescent whitening agent in the curable resin composition, a high reflectance can be achieved in the cured coating film thereof.
The fluorescent whitening agent absorbs light with the wavelength of 200-400 nm and releases light with the wavelength of 400-500 nm. Examples of such fluorescent dyes include: benzoxazole derivatives, coumarin derivatives, styryl biphenyl derivatives, pyrazolone derivatives, bis (triazinylamino) stilbene disulfonic acid derivatives, and the like. Among them, benzoxazole derivatives are preferable. As the substituent group of the benzoxazole derivative, a butyl group, an octyl group, a naphthyl group, a thienyl group, and a stilbene group are preferable.
The amount of the fluorescent whitening agent (C) in the composition of the present invention is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, based on 100 parts by mass of the curable resin (a). By making the compounding amount of the (C) fluorescent whitening agent within the above range, high reflectance can be achieved.
[ (D) at least any one selected from isocyanate compounds and coupling agents ]
The curable resin composition of the present invention contains (D) at least one selected from an isocyanate compound and a coupling agent. By containing (D) at least one selected from the group consisting of isocyanate compounds and coupling agents, the absorption by the fluorescent whitening agent at 400 to 420nm can be further promoted, and the effect of the fluorescent whitening agent at 440 to 470nm, that is, the improvement of the reflectance can be promoted.
((D-1) isocyanate Compound)
As the (D-1) isocyanate compound, known isocyanate compounds such as a monoisocyanate compound having 1 isocyanate group and a polyisocyanate compound having 2 isocyanate groups can be used. In the present invention, a blocked isocyanate compound is preferable from the viewpoint of improving the handling property due to excellent storage stability.
As the polyisocyanate compound, for example, aromatic polyisocyanate, aliphatic polyisocyanate and alicyclic polyisocyanate can be used.
Examples of the aromatic polyisocyanate include: 4, 4' -diphenylmethane diisocyanate, 2, 4-toluene diisocyanate, 2, 6-toluene diisocyanate, naphthalene-1, 5-diisocyanate, o-xylene diisocyanate, m-xylene diisocyanate, diphenylmethylene diisocyanate and 2, 4-toluene diisocyanate dimer.
Examples of the aliphatic polyisocyanate include: tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethylhexamethylene diisocyanate, 4-methylenebis (cyclohexyl isocyanate) and isophorone diisocyanate.
Specific examples of the alicyclic polyisocyanate include: bicycloheptane triisocyanate. Further, there may be mentioned adducts, biuret bodies and isocyanurate bodies of the above-exemplified isocyanate compounds.
The blocked isocyanate group contained in the blocked isocyanate compound is a group in which an isocyanate group is protected by a reaction with a blocking agent and thus temporarily inactivated. When heated to a predetermined temperature, the blocking agent is dissociated to generate an isocyanate group.
As the blocked isocyanate compound, an addition reaction product of an isocyanate compound and an isocyanate blocking agent may be used. Examples of the isocyanate compound capable of reacting with the blocking agent include the polyisocyanate compounds described above.
Examples of the isocyanate blocking agent include phenol blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol, lactam blocking agents such as e-caprolactam, d-valerolactam, y-butyrolactam and β -propiolactam, active methylene blocking agents such as ethyl acetoacetate and acetylacetone, alcohol blocking agents such as methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate, oxime blocking agents such as formaldoxime, acetaldoxime, acetoxime, methylethylketoxime, diacetylmonoxime and cyclohexyloxime, thiol blocking agents such as butylmercaptan, hexylmercaptan, t-butylmercaptan, thiophenol, methylphenthiophenol and ethylthiophenol, acid amide blocking agents such as acetic amide and benzamide, imide blocking agents such as succinimide and maleimide, amine blocking agents such as xylidine, aniline, butylamine, imidazole blocking agents, 2-ethylpropyleneimine blocking agents, and pyrazoline blocking agents such as maleimide, and maleimide blocking agents.
Examples of the blocked isocyanate compound include commercially available products such as: sumidur (registered trademark) BL-3175, BL-4165, BL-1100, BL-1265, Desmodur (registered trademark) TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, DESMOTHERM 2170, DESMOTHER 2265 (all Sumitomo Bayer Urethane Co., manufactured by Ltd.), CORONATE (registered trademark) 2512, CORONATE 2513, CORONATE 2520 (all Nippon polyurethane Industry Co., manufactured by Ltd.), B-830, B-815, B-846, B-870, B-874, B-882 (all manufactured by Mitsui Kogyo Katsu chemical Co., Ltd.), Duronate SBN-70D, TPA-B80E, 17B-60, E402-B80T (all Kahiasei chemical Corporation), TRIENE 7982, TRIENE 7951, TRIENE BI7951, TRIENE 7951, and/or the like), among them, Duranate SBN-70D and TRIXENE BI 7982 are preferable. Sumidur BL-3175 and BL-4265 were obtained by using methylethyloxime as a blocking agent.
Such isocyanate compounds may be used alone or in combination of 2 or more.
((D-2) coupling agent)
As the (D-2) coupling agent, a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, an aluminum coupling agent, or the like can be used. In particular, in the present invention, a silane coupling agent can be suitably used.
The silane coupling agent is a compound composed of an organic substance (organic group) and silicon, and is usually represented by XnR' (n-1) Si — R ″ -Y (X ═ hydroxy, alkoxy, and the like, and Y ═ vinyl, epoxy, styryl, methacryloyloxy, acryloxy, amino, ureido, chloropropyl, mercapto, polysulfide, isocyanate, and the like). Silane coupling agents have 2 or more different reactive groups in the molecule, and therefore, function as intermediaries between organic materials and inorganic materials, which are very difficult to link in general, and are used for strength improvement of composite materials, modification of resins, surface modification, and the like.
Specific examples of the silane coupling agent are as follows.
Examples thereof include N-gamma- (aminoethyl) -gamma-aminopropyltriethoxysilane, N-gamma- (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldiethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropylphenyldiethoxysilane, 2-amino-1-methylethyltriethoxysilane, N-methyl-gamma-aminopropyltriethoxysilane, N-phenyl-gamma-aminopropyltriethoxysilane, N-butyl-gamma-aminopropylmethyldiethoxysilane, N- β - (aminoethyl) -gamma-aminopropyltriethoxysilane, N- β - (aminoethyl) -N- β - (aminoethyl) -gamma-aminopropyltrimethoxysilane, gamma-ureidopropyltriethoxysilane, gamma-glycidoxypropyltriethoxysilane, gamma-glycidoxypropylmethyldimethoxysilane (3-glycidoxypropylmethyldimethoxysilane), β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-mercaptopropylmethyldimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 2-glycidoxypropyltrimethoxysilane, 3-methacryloyloxyethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, gamma-glycidyloxyethyltrimethoxysilane, 3-glycidyloxyethyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-glycidyloxypropyltrimethoxysilane, 3-glycidyloxyethyltrimethoxysilane, etc., preferably.
Examples of commercially available silane coupling agents include: KA-1003, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM-502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBE-603, KBM-903, KBE-9103, KBM-573, KBM-575, KBM-6123, KBE-585, KBM-703, KBM-802, KBM-803, KBE-846, KBE-9007 (trade names; manufactured by Shin-Etsu Chemical Co., Ltd.), etc. These may be used alone, or in combination of 2 or more.
The total amount of the (D-1) isocyanate compound and the (D-2) coupling agent in the composition of the present invention is preferably 0.01 to 50 parts by mass, more preferably 0.2 to 30 parts by mass, based on 100 parts by mass of the (A) curable resin. In the case of (D-1) isocyanate compound, it is more preferably 0.2 to 20 parts by mass, and in the case of (D-2) coupling agent, it is more preferably 0.2 to 25 parts by mass, particularly preferably 0.2 to 15 parts by mass. When the total amount of the (D-1) isocyanate compound and the (D-2) coupling agent is in the above range, both high reflectance and storage stability can be achieved.
[ (E-1) curing agent and (E-2) curing catalyst)
When the thermosetting resin (A-1) is used in the composition of the present invention, at least one of the curing agent (E-1) and the curing catalyst (E-2) may be further added.
Examples of the (E-1) curing agent include: polyfunctional phenol compounds, polycarboxylic acids and anhydrides thereof, aliphatic or aromatic primary or secondary amines, polyamide resins, polymercapto compounds, and the like. Among them, the polyfunctional phenol compound, and the polycarboxylic acid and the anhydride thereof can be preferably used in view of handling properties and insulating properties.
The polyfunctional phenol compound may be any compound having 2 or more phenolic hydroxyl groups in one molecule, and any known and conventional compound may be used. Specifically, there may be mentioned: phenol novolac resins, cresol novolac resins, phenol a, allylated bisphenol a, bisphenol F, bisphenol a novolac resins, and vinyl phenol copolymer resins, and phenol novolac resins are particularly preferred because of their high reactivity and high heat resistance-improving effect. Such a polyfunctional phenol compound may be subjected to addition reaction with at least either one of an epoxy compound and an oxetane compound in the presence of an appropriate curing catalyst.
The polycarboxylic acid and the acid anhydride thereof are compounds having 2 or more carboxyl groups in one molecule and acid anhydrides thereof, and examples thereof include: copolymers of (meth) acrylic acid, copolymers of maleic anhydride, condensates of dibasic acids, and the like. Examples of commercially available products include: JONCRYL (trade name) manufactured by BASF JAPAN LTD, SMA resin (trade name) manufactured by Sartomer Company, polyanhydride (polyazelaic polyanhydide) manufactured by Nippon chemical Co., Ltd.
The curing catalyst (E-2) is a compound capable of acting as a curing catalyst in the reaction between the curing agent (E-1) and at least one of an epoxy compound and an oxetane compound, or a compound capable of acting as a polymerization catalyst when no curing agent is used. Specific examples of the curing catalyst include: tertiary amines, tertiary amine salts, quaternary onium salts, tertiary phosphines, crown ether complexes, phosphine ylides (phosphine ylides), and the like, and any of these may be used alone or in combination of 2 or more.
Among them, particularly, there can be suitably mentioned: imidazoles such as imidazole having trade names of 2E4MZ, C11Z, C17Z and 2PZ, AZINE compounds such as imidazole having trade names of 2MZ-A and 2E4MZ-A, isocyanurates of imidazole such as 2MZ-OK and 2PZ-OK, imidazole methylol substrates such as 2PHZ and 2P4MHZ (trade names are all manufactured by Kagaku Kogyo Co., Ltd.), dicyandiamide and derivatives thereof, melamine and derivatives thereof, diaminomaleonitrile and derivatives thereof, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, bis (hexamethylene) triamine, triethanolamine, diaminodiphenylmethane, amines such as organic dihydrazide, 1, 8-diazabicyclo [5,4,0] -7-undecene (trade name is DBU, San-Apro Ltd.), 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecane (trade name ATU, manufactured by KIRIYAKU Co., Ltd.), and organic phosphine compounds such as triphenylphosphine, tricyclohexylphosphine, tributylphosphine, and methyldiphenylphosphine.
The amount of at least one of the curing agent (E-1) and the curing catalyst (E-2) is sufficient in a usual ratio, and is preferably 0.01 to 40 parts by mass, more preferably 0.05 to 30 parts by mass, based on 100 parts by mass of the thermosetting resin (A-1).
[ (F) antioxidant ]
The composition of the present invention preferably further contains (F) an antioxidant. By containing (F) an antioxidant, the effects of preventing oxidative deterioration of a curable resin and the like and suppressing discoloration can be obtained, and the effects of improving heat resistance and improving resolution (line width reproducibility) can also be obtained. That is, depending on the type of the white colorant (B), the resolution may be deteriorated by reflection or absorption of light, and by including the antioxidant (F), a good resolution can be obtained regardless of the type of the white colorant (B).
(F) The antioxidant may contain a radical scavenger for neutralizing the generated radical, a peroxide decomposing agent for decomposing the generated peroxide into harmless substances, a peroxide decomposing agent for not generating a new radical, and the like, and may be used singly or in combination of 2 or more.
Specifically, examples of the (F) antioxidant which functions as a radical scavenger include: phenol compounds such as hydroquinone, 4-t-butylcatechol, 2-t-butylhydroquinone, hydroquinone monomethyl ether, 2, 6-di-t-butyl-p-cresol, 2-methylene-bis (4-methyl-6-t-butylphenol), 1, 3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3, 5-trimethyl-2, 4, 6-tris (3, 5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3, 5-tris (3 ', 5' -di-t-butyl-4-hydroxybenzyl) -s-triazine-2, 4,6- (1H,3H,5H) trione, p-methoxyphenol, benzoquinone and the like, quinone compounds such as hydroquinone, and the like, And amine compounds such as bis (2,2,6, 6-tetramethyl-4-piperidyl) -sebacate and phenothiazine. Examples of commercially available products include IRGANOX1010 (trade name, manufactured by BASF Japan ltd).
Further, examples of the (F) antioxidant which functions as a peroxide decomposer include: phosphorus compounds such as triphenyl phosphate, and sulfur compounds such as pentaerythritol tetralauryl thiopropionate, dilauryl thiodipropionate, distearyl 3, 3' -thiodipropionate.
Among the above, the phenol-based antioxidant is preferably used from the viewpoint of further obtaining the effect of suppressing discoloration, improvement in heat resistance, and good resolution.
When the antioxidant (F) is used, the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.03 to 5 parts by mass, per 100 parts by mass of the curable resin (a). By setting the amount of the antioxidant (F) to 0.01 parts by mass or more, the effect of the addition of the antioxidant can be obtained reliably, while by setting the amount to 10 parts by mass or less, good alkali developability can be obtained without inhibiting photoreaction, and good finger-touch dryness and coating film properties can be ensured.
In addition, the antioxidant (F), particularly a phenol-based antioxidant, may exhibit further effects when used in combination with a heat-resistant stabilizer, and therefore the resin composition of the present invention may contain a heat-resistant stabilizer.
Examples of the heat stabilizer include: phosphorus-based, hydroxylamine-based, and sulfur-based heat stabilizers. The heat stabilizer may be used singly or in combination of 2 or more.
The composition of the present invention may contain a photo-excitable inorganic filler. Examples of the photoexcitable inorganic filler include: strontium aluminate, zinc sulfide and the like, and in particular, strontium aluminate can be suitably used. In addition, the photo-excitable inorganic filler is preferably subjected to surface treatment with an inorganic component or an acidic liquid in order to improve the reflectance of the cured coating film. As the inorganic component used for the surface treatment, there may be mentioned: silica (glass), alumina, zirconia, and the like. As the method of surface treatment using an inorganic component, a known method can be used, and there is no particular limitation.
The composition of the present invention may contain a photopolymerization initiator. In particular, when the photocurable resin (A-2) is used, a photopolymerization initiator is preferably added.
Among the photopolymerization initiators, acylphosphine oxide type photopolymerization initiators such as bisacylphosphine oxides and monoacylphosphine oxides are preferable because they are less adhesive and have an excellent discoloration-inhibiting effect.
The composition of the present invention may contain a reactive diluent solvent. The reactive diluent solvent is used for adjusting the viscosity of the composition to improve the handling property, and for improving the crosslinking density or the adhesion, and a photocurable monomer or the like can be used. As the photocurable monomer, the above photopolymerizable vinyl monomer and the like can be used.
The composition of the present invention may contain an organic solvent for preparing the composition and adjusting the viscosity when applied to a substrate or a carrier film. As organic solvents, it is possible to use: ketones such as methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as toluene, xylene, and tetramethylbenzene; glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol diethyl ether, diethylene glycol monomethyl ether acetate, and tripropylene glycol monomethyl ether; esters such as ethyl acetate, butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and propylene carbonate; aliphatic hydrocarbons such as octane and decane; and petroleum solvents such as petroleum ether, naphtha, solvent naphtha, and the like. These organic solvents may be used alone or in combination of two or more.
Further, other additives conventionally used in the field of electronic materials may be blended in the composition of the present invention. Examples of other additives include: a thermal polymerization inhibitor, an ultraviolet absorber, a plasticizer, a flame retardant, an antistatic agent, an anti-aging agent, an antibacterial/antifungal agent, a defoaming agent, a leveling agent, a filler, a thickener, an adhesion imparting agent, a thixotropy imparting agent, another colorant, a photo-initiation aid, a sensitizer, a curing accelerator, a mold release agent, a surface treating agent, a dispersant, a dispersing aid, a surface modifier, a stabilizer, a phosphor, and the like.
The curable resin composition of the present invention may be used in the form of a dry film or in the form of a liquid. When used in a liquid form, the polymer may be of a one-pack type or a two-pack type or more. In particular, when the two-component type is formed, the components (a) to (D) may be blended into the same formulation or may be blended into different formulations.
Next, the dry film of the present invention has a resin layer obtained by coating and drying the composition of the present invention on a carrier film. To form a dry film, the composition of the present invention is first diluted with the above-mentioned organic solvent to adjust to an appropriate viscosity, and then coated on a carrier film to a uniform thickness by means of a comma coater (comma coater), a knife coater, a lip coater (lip coater), a rod coater (rod coater), a squeeze coater (squeeze coater), a reverse coater (reverse coater), a transfer roll coater (transfer roll coater), a gravure coater (gravure coater), a spray coater, or the like. Then, the coated composition is dried at a temperature of 50 to 130 ℃ for 1 to 30 minutes, so that a resin layer can be formed. The coating film thickness is not particularly limited, and is usually selected appropriately within a range of 10 to 150 μm, preferably 20 to 60 μm, in terms of the film thickness after drying.
As the carrier film, a plastic film, for example, a polyester film such as polyethylene terephthalate (PET), a polyimide film, a polyamideimide film, a polypropylene film, a polystyrene film, or the like can be used. The thickness of the carrier film is not particularly limited, and is usually appropriately selected within a range of 10 to 150 μm.
After forming a resin layer made of the composition of the present invention on a carrier film, a peelable cover film is preferably further laminated on the surface of the film in order to prevent adhesion of dust and the like to the surface of the film. As the peelable cover film, for example, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, a surface-treated paper, or the like can be used. The cover film may be one having a lower adhesive force between the resin layer and the carrier film when the cover film is peeled.
In the present invention, the resin layer may be formed by applying the composition of the present invention on the protective film and drying the composition, and the carrier film may be laminated on the surface of the resin layer. That is, in the present invention, when a dry film is produced, either a carrier film or a protective film can be used as a thin film to which the composition of the present invention is applied.
For example, the composition of the present invention is adjusted to a viscosity suitable for a coating method using the organic solvent, and is applied to a substrate by a method such as dip coating, flow coating, roll coating, bar coating, screen printing, or curtain coating, and then the organic solvent contained in the composition is evaporated and dried (temporarily dried) at a temperature of about 60 to 100 ℃. In addition, when the composition is applied to a carrier film or a protective film, dried to form a film, and taken up to obtain a dry film, the composition of the present invention is laminated to a substrate so that a layer thereof is in contact with the substrate using a laminator or the like, and then the carrier film is peeled off to form a resin layer.
Examples of the substrate include, in addition to a printed wiring board and a flexible printed wiring board on which a circuit is formed in advance with copper or the like, a copper-clad laminate of all grades (e.g., FR-4) using a material such as a copper-clad laminate for high-frequency circuits using paper-phenol resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabric-epoxy resin, glass cloth/paper-epoxy resin, synthetic fiber-epoxy resin, fluorine resin, polyethylene, polyphenylene oxide (polyphenylene oxide) cyanate ester, or the like, a metal substrate, a polyimide film, a PET film, a polyethylene naphthalate (PEN) film, a glass substrate, a ceramic substrate, a wafer plate, and the like.
The volatilization drying after the application of the composition of the present invention can be carried out by using a hot air circulation type drying oven, an IR oven, a hot plate, a convection oven, or the like (a method of bringing hot air in a dryer into convection contact by using a device having a heat source of an air heating system using steam and a method of blowing the hot air to a support through a nozzle).
The composition of the present invention can be heated to a temperature of about 100 to 180 ℃ to thermally cure the composition, thereby forming a cured coating (cured product) having excellent properties such as heat resistance, chemical resistance, moisture absorption resistance, adhesion, and electrical properties.
After the composition of the present invention is applied and the solvent is evaporated and dried, the obtained resin layer is exposed (irradiated with light), and the exposed portion (portion irradiated with light) is cured. Specifically, a resist pattern can be formed by selectively exposing an active energy ray through a photomask having a pattern formed thereon by a contact or non-contact method, or by directly exposing the pattern by a laser direct exposure machine, and developing the unexposed portion with a dilute alkali aqueous solution (for example, a 0.3 to 3 mass% sodium carbonate aqueous solution).
As the exposure device for irradiating the active energy ray, a device equipped with a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a metal halide lamp, a mercury short arc lamp, or the like and irradiating ultraviolet rays in the range of 350 to 450nm may be used, and a direct drawing device (for example, a laser direct imaging device for directly drawing an image with a laser beam by CAD data from a computer) may be used. As a lamp light source or a laser source of the line drawing machine, the maximum wavelength is within the range of 350-410 nm. The exposure amount for forming an image varies depending on the film thickness, etc., and is usually 20 to 800mJ/cm2Preferably 20 to 600mJ/cm2Within the range of (1).
As the developing method, a dipping method, a rinsing method, a spraying method, a brush coating method, and the like can be used, and as the developer, an alkaline aqueous solution of potassium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines, and the like can be used.
The composition of the present invention is suitably used for forming a cured coating film on a printed wiring board, more preferably for forming a permanent coating film, and further preferably for forming a solder resist layer or a cover layer. The curable resin composition of the present invention can also be used for forming a bank (Solder Dam). The composition of the present invention is white, and thus can be suitably used for a reflector for reflecting light emitted from a Light Emitting Diode (LED) or Electroluminescence (EL) used as a light source of a backlight of a liquid crystal display such as a lighting device, a portable terminal, a computer, or a television.
Examples
The present invention will be described in more detail below with reference to examples.
Synthesis of curable resin (varnish A) (A-1-1)
A2000 ml flask equipped with a stirrer and a condenser was charged with 431g of dipropylene glycol monomethyl ether, and the mixture was heated to 90 ℃ under a nitrogen stream. A sample prepared by mixing and dissolving 104.2g of styrene, 296.6g of methacrylic acid, and 23.9g of dimethyl 2, 2' -azobis (2-methylpropionate) (Wako pure chemical industries, Ltd.: V-601) was added dropwise to the flask over 4 hours.
Thus, a non-photosensitive carboxyl group-containing resin varnish A as the curable resin (A-1) was obtained. The non-photosensitive carboxyl group-containing resin varnish A had an acid value of the solid content of 140mgKOH/g and a solid content of 50% by mass.
Synthesis of (A-2-1) curable resin (varnish B)
In a flask equipped with a thermometer, a stirrer, a dropping funnel and a reflux condenser, 325.0 parts by mass of dipropylene glycol monomethyl ether as a solvent was heated to 110 ℃, a mixture of 174.0 parts by mass of methacrylic acid, 174.0 parts by mass of ∈ -caprolactone-modified methacrylic acid (average molecular weight 314), 77.0 parts by mass of methyl methacrylate, 222.0 parts by mass of dipropylene glycol monomethyl ether and 12.0 parts by mass of t-butylperoxy 2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION) as a polymerization catalyst was added dropwise over 3 hours, and further stirred at 110 ℃ for 3 hours to deactivate the polymerization catalyst, thereby obtaining a resin solution. After cooling the resin solution, CYCLOMER M100289.0 parts by mass, which was manufactured by Daicel Corporation, 3.0 parts by mass of triphenylphosphine and 1.3 parts by mass of hydroquinone monomethyl ether were added thereto, and the mixture was heated to 100 ℃ and stirred to cause ring-opening addition reaction of the epoxy group, thereby obtaining a photosensitive carboxyl group-containing resin varnish B.
The photosensitive carboxyl group-containing resin varnish B thus obtained had a solid content of 45.5% by mass and an acid value of the solid matter of 79.8 mgKOH/g. The weight average molecular weight (Mw) of the solid content of the obtained photosensitive carboxyl group-containing resin varnish B was 15000.
The respective components were blended according to the formulation shown in the following table, premixed by a mixer, dispersed by a three-roll mill, and kneaded to prepare respective compositions. For example 19 and comparative example 5, prepared were a liquid a (one-pack type) and a liquid B (two-pack type). The compounding amounts in the tables represent parts by mass.
The compositions of the respective examples and comparative examples thus obtained were evaluated as follows. In example 19 and comparative example 5, the liquid a and the liquid B were mixed sufficiently at a ratio of 8:2 in the production of substrates. The results are shown in the following table.
(1) Reflectivity of light
The composition described in comparative example 3 was applied to FR-4 material by screen printing over the entire surface, dried in a hot air circulating drying oven at 80 ℃ for 30 minutes, cooled to room temperature, and then heated at 600mJ/cm2The substrate was exposed to light through a negative mask, developed under 0.2MPa for 90 seconds, washed with water, and then cured after curing at 150 ℃ for 60 minutes to give a cured coating film. Then, the compositions described in examples 1 to 17 and 19 and comparative examples 1 to 2 and 5 were applied to the entire surface of the cured coating film by screen printing, and cured in a hot air circulation type drying furnace at 150 ℃ for 30 minutes to obtain a substrate.
Further, the composition described in comparative example 3 was applied to FR-4 material by screen printing over the entire surface, dried in a hot air circulating drying oven at 80 ℃ for 30 minutes, cooled to room temperature, and then applied at 600mJ/cm2The substrate was exposed to light through a negative mask, developed under 0.2MPa for 90 seconds, washed with water, and then cured after curing at 150 ℃ for 60 minutes to give a cured coating film. However, the device is not suitable for use in a kitchenThen, the respective compositions described in example 18 and comparative examples 3 and 4 were applied to the cured coating film on the whole surface by screen printing, dried in a hot air circulation type drying oven at 80 ℃ for 30 minutes, and naturally cooled to room temperature. Exposing the substrate to light at an exposure of 600mJ/cm2The substrate was exposed to light through a negative mask, and developed with a 1 mass% aqueous solution of sodium carbonate at 30 ℃ under a spray pressure of 0.2MPa for 90 seconds and washed with water to obtain a developed substrate. Further, the resultant was cured at 150 ℃ for 60 minutes to obtain a substrate.
The reflectance at a wavelength of 450nm was measured with a spectrophotometer (CM-2600d, manufactured by KONICA MINOLASING, INC.) with respect to the coating film surface of each of the obtained substrates.
In addition, the compositions of examples 2 and 3 and comparative example 2 were measured for reflectance in the wavelength range of 420 to 470nm in the same manner. The results are shown in the graph of fig. 1.
(2) Resistance to welding heat
The compositions described in examples 1 to 17 and 19 and comparative examples 1 to 2 and 5 were applied to an FR-4 material over the entire surface by screen printing, and cured in a hot air circulation type drying furnace at 150 ℃ for 30 minutes to obtain a substrate. The compositions described in example 18 and comparative examples 3 and 4 were applied to the FR-4 material over the entire surface by screen printing, dried in a hot air circulation type drying oven at 80 ℃ for 30 minutes, and naturally cooled to room temperature. Exposing the substrate to light at an exposure of 600mJ/cm2The substrate was exposed to light through a negative mask, and developed with a 1 mass% aqueous solution of sodium carbonate at 30 ℃ under a spray pressure of 0.2MPa for 90 seconds and washed with water to obtain a developed substrate. Further, the resultant was cured at 150 ℃ for 60 minutes to obtain a substrate. Each of the obtained substrates was coated with a rosin-based flux, immersed in a solder bath set at 260 ℃ in advance, washed with a modified alcohol, and then evaluated for swelling and peeling of the resist layer by visual observation. The criteria for determination are as follows.
○ No peeling was observed even if the dipping was repeated 3 times or more for 10 seconds.
X: the resist layer was immersed for 10 seconds within 3 times, and swelling and peeling occurred.
(3) Storage stability
An appropriate amount of each composition was charged into a plastic container having a capacity of 30g, stored at 10 ℃ or lower for 180 days, and the state of the composition after storage was visually evaluated. In example 19 and comparative example 5, appropriate amounts of liquid a and liquid B were placed in plastic containers each having a capacity of 30g, and stored at i)10 ℃ or lower for 180 days and ii)30 ℃ or lower for 180 days, respectively, and the states of liquid a and liquid B after storage were visually evaluated. The criteria for determination are as follows.
○ No gelling occurred.
X: gelation occurred.
-: not evaluated
[ Table 1]
[ Table 2]
[ Table 3]
1) non-photosensitive carboxyl group-containing resin varnish A (values in the Table are values of solid content)
"2") non-photosensitive carboxyl group-containing resin varnish (values in the table are values of solid content), LUMIFLON200F, manufactured by Asahi glass company Ltd. (fluororesin varnish)
3) non-photosensitive carboxyl group-containing resin varnish (values in the table are values of solid content), X-22-3701E, product of shin Etsu chemical Co., Ltd. (Silicone resin varnish)
4) titanium oxide (TIPAQUE CR-58, rutile type titanium oxide produced by the chlorine method, available from Shidai Kagaku K.K.)
5) titanium oxide (TIPAQUE R-820, rutile type titanium oxide produced by sulfuric acid method, available from Shidai Kagaku K.K.)
Titanium oxide (TiONA 696, rutile type titanium oxide produced by the chlorine method, available from CRYSTAL CORPORATION)
7) NIKKAFLUOR SB conc., manufactured by Nippon Chemical Industrial Co., Ltd
8) LXS FBW MAN 01, manufactured by Lanxess Corporation
9) Tinopal OBCO, BASF JAPAN LTD
10) blocked isocyanate compound (TRIXENE BI 7982, manufactured by Baxeneden Chemicals Limited), solid content: 70% by mass of a liquid at room temperature
11) blocked isocyanate compound (Duranate SBN-70D, manufactured by Asahi Kasei chemicals corporation), solid content: 70% by mass of a liquid at room temperature
12) silane coupling agent (KBM-402, 3-glycidoxypropylmethyldimethoxysilane, Shin-Etsu chemical Co., Ltd., manufactured by Ltd.) which is liquid at room temperature
13) silane coupling agent (KBM-5103, 3-acryloxypropyltrimethoxysilane, Shin-Etsu chemical Co., Ltd.) liquid at room temperature
14) IRGANOX1010 (phenolic), BASF JAPAN LTD
15) KS-66, Shin-Etsu Chemical Co., Ltd
16) Disperbyk-111, BYK Japan KK
17) TEPIC-HP, manufactured by Nissan chemical industries, Ltd
18) dicyandiamide (curing catalyst)
19) Melamine-Tetrahydrophthalate (curing catalyst), manufactured by Nissan chemical industries, Ltd
20) AEROSIL R-974, NIPPON AEROSIL co, ltd
21) LMP-100, manufactured by Fuji Talcum Industrial Co Ltd
22) MFTG (tripropylene glycol monomethyl ether), Nippon Nyukazai co
23) DPM (dipropylene glycol monomethyl ether)
24) Melamine (curing catalyst)
25) DA-600 (manufactured by Sanyo Chemical Industries, Ltd.)
26) photosensitive carboxyl group-containing resin varnish B (values in the table are values of solid content)
27)' IRGACURE TPO (manufactured by BASF JAPAN LTD.)
From the results of examples 1 to 18 in the table, it is understood that the curable resin composition containing the white colorant and at least one of the fluorescent whitening agent and the isocyanate compound and the coupling agent has improved reflectance while maintaining the soldering heat resistance and the storage stability. On the other hand, it is clear from the results of comparative examples 1 to 4 that the curable resin composition lacking any one of the components of the present invention is inferior in reflectance. From the results of example 19, it is understood that the curable resin composition of the present invention can maintain the soldering heat resistance and the storage stability even in the two-component type, and has an improved reflectance, and particularly has excellent storage stability even under severe conditions. On the other hand, from the results of comparative example 5, it is clear that the curable resin composition lacking any of the components of the present invention has a poor reflectance even in the two-component type.
Claims (4)
1. A curable resin composition characterized by containing (A) a curable resin containing a carboxyl group-containing resin, (B) a white colorant, (C) a fluorescent whitening agent, and (D) at least one member selected from the group consisting of isocyanate compounds and coupling agents.
2. A dry film comprising a resin layer obtained by applying the curable resin composition according to claim 1 to a film and drying the applied film.
3. A cured product obtained by curing the curable resin composition or the resin layer according to claim 1, wherein the resin layer is obtained by applying the curable resin composition according to claim 1 and drying the applied resin layer.
4. A printed wiring board comprising the cured product according to claim 3.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015-074201 | 2015-03-31 | ||
| JP2015074201 | 2015-03-31 | ||
| PCT/JP2015/080454 WO2016157587A1 (en) | 2015-03-31 | 2015-10-28 | Curable resin composition, dry film, cured object, and printed wiring board |
Publications (2)
| Publication Number | Publication Date |
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| CN107406681A CN107406681A (en) | 2017-11-28 |
| CN107406681B true CN107406681B (en) | 2020-02-07 |
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| Country | Link |
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| JP (1) | JP6684779B2 (en) |
| KR (1) | KR102456796B1 (en) |
| CN (1) | CN107406681B (en) |
| WO (1) | WO2016157587A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3308956B1 (en) * | 2016-10-14 | 2021-07-07 | Senoplast Klepsch & Co. GmbH | Thermally moldable panel |
| KR20200140290A (en) | 2018-03-30 | 2020-12-15 | 다이요 잉키 세이조 가부시키가이샤 | Curable composition, cured product thereof, and electronic component having the same |
| JP6962958B2 (en) * | 2019-03-25 | 2021-11-05 | 株式会社タムラ製作所 | Photosensitive resin composition |
| KR102398123B1 (en) * | 2020-06-10 | 2022-05-17 | 한국다이요잉크 주식회사 | Solder resist resin composition, solder resist structure, dry film, and printed wiring board |
| CN111650811B (en) * | 2020-06-18 | 2024-01-26 | 上海孚赛特新材料股份有限公司 | White photosensitive film and preparation method and application thereof |
| CN111999982A (en) * | 2020-09-09 | 2020-11-27 | 广州斯达利电子原料有限公司 | Light-sensitive polyacrylic resin for LED light-sensitive solder-resistant white oil and preparation method thereof |
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- 2015-10-28 JP JP2017509149A patent/JP6684779B2/en active Active
- 2015-10-28 CN CN201580078123.XA patent/CN107406681B/en active Active
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- 2015-10-28 KR KR1020177030968A patent/KR102456796B1/en active IP Right Grant
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102456796B1 (en) | 2022-10-21 |
| JP6684779B2 (en) | 2020-04-22 |
| JPWO2016157587A1 (en) | 2018-01-25 |
| CN107406681A (en) | 2017-11-28 |
| WO2016157587A1 (en) | 2016-10-06 |
| KR20170132815A (en) | 2017-12-04 |
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